Photocurable polishing wax containing a polyene-polythiol resin

ABSTRACT

A photocurable polishing wax having the following composition; (a) 1 part of a polyene having at least two unsaturated carbon to carbon bonds per molecule; (b) about 0.2-1 part of a nonionic emulsifier; (c) about 0.1-0.9 part of carnauba wax, paraffin wax, or a mixture thereof; (d) about 1-50 parts water; (e) a quantity of a liquid polythiol component having at least 2 thiol groups per molecule to provide about 0.6-1.1 equivalents of polythiol per equivalent of the polyfunctional component, the total functionality of the polyene and the polythiol being greater than 4; and (f) about 0.05-0.25 part of a photocuring rate accelerator.

QQRT OF CORR @Ii LASJZ PAGE Wrzesinski 45: Dec. 10, 1974 1 1 PHOTOCURABLE POLISHING WAX [561 References Cited CONTAINING A POLYENE-POLYTHIOL UNITED STATES PATENTS RESIN 3.328.325 6/1967 zdano'askinmmmnn"... 260/22 1nventor: Joseph Francis Wrzesinski,

Baltimore, Md.

Astignee: W. R. Grace & C0., New York,

med: Sept. 21, 1913 Appl. No; 401,312

Re1ated U.S. Application Data Continuation-impart of Ser. No. 316,766, Dec. 20 1972, abandoned, which is a continuation-in-part of Ser. No. 276,300. July 31, 1972, abandoned.

US. CL 204/159J8, 96/115 F, 117/9331,

3,661,744 5/1972 Kchr :t 21. 204115914 Primary Examiner-Paul Lieberman Assistant Examiner-Richard 8. Tuner Attorney, Agent, or FrmE1ton Fshex: Kenneth E. Prince [57] ABSTRACT A photoeurable poEhing wax having the following mposition; (a) 1 mrt of a poi s ene having at least two umaturated carbon to cat-bo n bonds per molecu1e; (b) about 0.2-1 part of a noronic emtflsifiet; (c) about 0.1-0.9 part of camauba m paraffin wax, or a mixture thereof; (d) about 1-50 parts water, (e) a quantity of a liquid po1ythio1 component having at least 2 :hiol groups per molecuEe to provide about 0.6-4-1 equivalents of polythiol per equivalent of the poiyfuncfional component, the total functionaiity of the polyene and the poiythlol being greater than 4; and (f) about 005-015 part of a pbotocuring rate acceierator.

14 Claims, No Drawings PHOTOCURABLE POLISHING WAX CONTAINING A POLYENE-POLYTHIOL RES'lN CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of application Ser. No.

316.766 filed Dec. 20, 1972 and now abandoned which was, in turn, a continuation-in-part of application Ser. No. 276,300 filed .Iuly 3l, 1972 and now abandoned.

BACKGROUND OF THE INVENTION This invention is in the field of polishing wax. More particularly it is in the field of photocurable polishing wax useful for protecting metal and other surfaces.

Wax compositions for polishing and protecting surfaces are well known to those skilled in the art.

The wax of this invention differs from those of the prior art in that it is a photocurable polishing wax comprising an aqueous dispersion having therein a polyfunctional component (a polyene) containing at least two reactive ethylenically unsaturated carbon-tocarbcn bonds per molecule and a polythiol having molecules containing at least two thiol groups per moleccle. the total functionality of the polyfunctional component and the polythiol being greater than 4. the polyfunctional component and the polythiol reacting in the presence of actinic light to produce a strong hard solid which adheres strongly to the surface on which the wax was applied. Sunlight provides ample actinic radiation to produce a cure (i.e.. to cause the polyfunctional component and the polythiol to react to form the aforesaid hard solid which adheres strongly to the surface to which the wax composition was applied as a thin coating or film having a thickness of about 0.01-05 mil) within about l-30 minutes.

US. Pat. No. 3.328.325 (Zdanowski, 260/22) teaches a polishing wax comprising a polymer. However, the wax of Zdanowski differs from the wax of this invention in that Zdanowskis wax contains a polymer per se while the wax of this invention contains precursors (the polyene and the polythiol) which react where exposed to actinic light (after the wax has been applied to a surface to be protected) to form a polymer which adheres to said surface.

SUMMARY OF THE INVENTION In summary. this invention is directed to a photocurable polishing wax consisting essentially of: a. 1 part of a'polyene having the formula i. R is a hydrocarbyl radical having about l2-l00 (preferably about 12-60) Carbon atoms.

ii. E is hydrogen or CH,-CH=CH,; and

iii. :1 is an integer from 2 to 9.

in which;

i i. R, is a hydrocarbyl radical having about 6-50 (preferably-6-30) carbon atoms; ii. x is an integer from to 9; and iii. y is an integer from 2' to to provide about 0.6-1.1 (preferable about 0.8-1.1 or 0.8-0.95) equivalents of polythiol per equivalent of the polyene, the total functionality of the polyene and the polythiol being greater than 4; and f. 0.05-0.25 (preferable ODS-0.1. or 0.050.2 or 0.06-0.l) part of a photocuring rate accelerator. In addition to the above-listed components the photocuring polishing wax of this invention can contain additives such as; (a) beeswax (e.'g.. about 0.l-5'parts per part of said polyfunctional component); (b) glycerol or a glycol such as ethylene glycol. propylene glycol. diethylene glycol. dipropylene glycol, or the like preferably about 0.l-3 parts per part of said polyfunctional component; (c) a silicone oil or silicone fluid (e.g.. about 0.1-1 part of a silicone oil having a viscosity of about 4-1500 (preferably 20-1000 or 90-200) centipoises at 25C per part of said polyfunctional component); and (d) a paraffin oil (e.g.. about 0.1-3 parts of a parafiin oil having a viscosity of about 500-l000 centipoises at 20C and a specific gravity of about 0.83-0.9 at 20C per part of said polyfunctional component).

DESCRIPTION OF THE PREFERRED EMBODIMENTS In preferred embodiments of the photocurable polishing wax of the above Summary:

I. The photocurable polishing wax contains about 5-25 percent (more preferably about l0-l5 percent) by weight of a water insoluble. abrasive. particulate filler based on the weight of the photocurable polishing wax plus filler. Especially preferred fillers include particulate calcium oxide. magnesium oxide. calcined dolonite; calcium hydroxide. hydrated magnesium oxide. hydrated calcined doiomite. CaCO clay. talc. mica. silica. alumina. titania. gypsum. glass. and the like. the particles being of such size that they will pass about a 100 mesh screen (or a 200 mesh screen or a 325 mesh screen). Because of my disclosure. other fillers will be readil, apparent too those skilled in the art.

2. The photocuring rate accelerator is selected from the group consisting of an aryl aldehyde. a diaryl ketone. an alkyl aryl ketone. a triaryl phosphine. a dialky! ketone. and a blend ofa carbon tetrahalide with a polynuclear aromatic hydrocarbon.

3. The wax is caranauba wax.

4. The wax is paraffin wax.

0 CIL CHCIEO ii 5- The wax is a mixture of caranauba wax and paraffin wax (more preferably about equal parts of each by weight).

6- The photocuring rate accelerator is benzophenone. 7; The polyene is (which can be formed by the reaction of a mole 4,4:

dicyclohexylmethane oiisocyanate with two moles of allyl alcohol-both of which are artiv cles of commerce) 8. The polythiol is pentaerythritol tetrakis(fi-mercap topropionate 9- The nonionic emulsifier is a polypropylene glycol), e.g., Pluronic F88,

K). The polyene is L ClhOclhCll=Clh (which can be made by the reaction of a mole of toluo-i-cthcm) i i- R is a hydrocarbyl radical having about 12-100 (pre erably l2-60) carbon atoms; ii. E is hydrogen or CH,--CH=CH,; and iii. n is an integer from 2 to 9; b. about 0.2-2 pans of a nonionic emulsifier;

y ypropylenepoiyoxyethylene emulsifier (which can be prepared by the reaction of ethylene oxide with c. about 0.1-0.9 parts of a wax selected from the group consisting of carnauba wax, a paraffin wax melting at about 4368C or a mixture thereof;

d. about 04lC'.9 parts of beeswax;

e. about 0.1-1 part of a silicone oil having a viscosity of 4-1.500 centipoises at 25C;

f. about 1-50 parts of water;

g. a quantity of a liquid polythiot having the formula i. R, is a hydrocarbyl radical having about 6-50 (preferable 6-30) carbon atoms; ii. x is an integer from 0 to 9; and iii. y is an integer from 2 to 5 to provide about 0.6-l .l equivalents of polythivol per equivalent of the polyene, the total functionality of the poiyene and the polythiol being greater than 4; and (h) 0.05-0.25 part of a photocurizetg rate accelerator. Silicone fluids or oils are wel known to those skilled in the art. They are described on pages 237-241 of Volume l8 of the Kirk-Othmer Encyclopedia of Chemical Technotogy. John Wily & Sons. lnc., New York. N. S. (2969) and on page 6l2 of the Seventh Edition of Smiths College Chemistry, Appleton-Century-Crofts. Inc.. (1960).

in an especially preferred embodiment the photocurable composition of Embodiment A supra, consists essentially of:

a. l part of a polyene having the formula L on, cmouacufln,

b. 1 part of Pluronic F88 a nonionic emulsifier prepared by the reaction of ethylene oxide with polypropylene glycol.

c. 0.5 part of carnauba wax;

d. 0.3 part of beeswax:

e. 0.5 part of a silicone oil having a viscosity of 90-200 centipoises at 25C;

f. 3.5-4 parts of water;

g. 0.6 part of pentaezythritol tetzakis (fl-mercaptopropionate); and i h. 0.08- 0.12 part of benzophenooe.

DETAILED DESCRlPTlON OF THE lNrENTTON it is an object of this invention to provide a composition of matter useful as a photocurable polishing wax excellently adapted to improve the appearance of and to protect metal surfaces, painted surfaces (including painted metal surfaces), and other surfaces (including wooden surfaces).

It is another object of this invention to provide a photocurable composition useful as a polishing wax which is excellently adapted to improve the appearance of and to protect surfaces and which can be readily cured by exposure to sunlight for about i 30 or 5-25 minutes or by exposure to actinic radiation having a wavelength of about 3000-4000 A.

Still other objects will be readily apparent to those skilled in the art.

These and other objects have been attained by: (l) basing the photocurable polishing wax on a photocurable composition (Composition A) consisting essentially of; (a) l part of a polyfunctional component (a polyene) containing at least two reactive ethylenically unsaturated carbon-to-carbon bonds per molecule; (b) a quantity of a liquid polythiol component having molecules containing at least two thiol groups per molecule to provide about 0.6l-l equivalent of polythiol per equivalent of the polyene (polyfunctional compound). the total functionality of the nolyfunctional compound and the polythiol being greater than 4. and (c) 0.05-0.25 part of a photocuring rate accelerator; and (2) incorporating other essential and optional ingredients of the polishing wax of my invention into-such composition A.

The following US. Patents teaching polyfunctiortal components (polyenes) containing at least two reactive unsaturated carbon-to-carbon bonds per molecule. polythiol components containing at least two thiol groups per molecule, photocuring rate accelerators and photocuring compositions comprising (or consisting essentially) of admixtures of such photocuring rate accelerators are incorporated herein by reference;

1. US. Pat. No. 3.6l5.450. Werber et al. 96/35-].

2 US. Pat. No. 3.645.730. Frank et al. 96128.

3. US. Pat. No. 3.537.853. Wessells et al. 96135.1.

4. US. Pat. No. 3.535.193. Prince. l6l/88.

5. US. Pat. No. 3.661.744. Kehr et al. 204115914.

6. US. Pat. No. 3.578.614. Wszolek. 260/l3.

7. US. Pat. No. 3.660.088. Lundsager. 96/36.

8. US. Pat. No. 3.662.022. Lard. 260/837 R.

9. US. Pat. No. 3.662.023. Kehr et al. 260/858- moieties. thiol moities. organometallic moieties. positive halogen moieties. and reactive unsaturated carbonto-carbon bonds-except the reactive unsaturated carbon-to-carbon present in the pendent groups:

in which E is defined in the above Summary.

it is aiso readily apparent tha. said hydrocarbyl moiety (R) can contain cyclic groupings and heter. atoms such as N. S. P or O and that it should generally contain primarily carbon-carbon. carbon-nitrogen. or carbonoxygen chain linkages.

It is further readily apparent that the hydrocarbyl moiety (hydrocarbyl radical). R of the polythiol used 10. U.S. Pat. No. 3.700.574. Kehr et al. 204/ 159.14.

As used herein the term reactive. as applied to an ethylenically unsaturated carbon-to-carbon bond. means that the ethylenically unsaturated bond will react under proper conditions as set forth herein with thiol groups to yield thioether linkage as contrasted to the term unreactive" carbon-t0 carbon unsaturation (i.e.. an unreactive carbon-tocarbon double bond) which means are it is readily apparent that the hydrocarbyl radical in preparing the composition of this invention is free of peroxide moieties. positive halogen moieties. organiometallic moieties. reactive unsaturated carbon-to- I carbon bonds. and thiol moieties-except the thiol moieties present in the pendent groups:

in which x is defined in the above Summary.

it is also readily apparent that said hydrocarbyl radical (R,) can contain cyclic groupings and minor amounts or hetero atoms such as N. S; P or 0 but primarily contains carbon-carbon. carbon-nitrogen. or carbon-oxygen chain linkages.

'Nonionic emulsifiers are well known to those skilled in the art. A large number of such emulsifiers. which can be used with excellent results in preparing the photocurable polishing wax of this invention. are described on pages l27-l3l of Volume 8 of the Second Edition of the Kirk- Othmer "Encyclopedia of Chemical Technology" (1969). The Pluronic surfactants (condensation products of ethylene oxide and polypropylene glycol). especially 'Pluronic R88. are preferred emulsifiers ing the composition of this invention is free of peroxide for use in preparing the photocurable polishing wax of this invention.

Where preparing a photocurable polishing wait of the instant invention I have usually foilowed a procedure comprising:

1. Forming a first mixture by admixing l part of the aforesaid polyfunctional component (polyene) containing at least two reactive unsaturated carbon-to-carbon bonds per molecule with about 015-05 part of a nonionic emulsifier.

2. Adjusting the temperature of the first mixture to about -90C. (if it is not already within this temperature range); vigorously agitating (e.g.. stirring at a rapid rate) the first mixture and adding hot (ca. 80"-90C.) water thereto while vigorously agitating the resulting second mixture and maintaining it at about 8090C. The water is added in increments of about 0.l to 0.3 part per part of the polyfunctional component until a total of about l -50 parts of water per part of the polyfunctional component has been added over a period of about 0.5-2 hours. 3. Maintaining the second mixture at about 8090C.

and continuing to agitate it vigorously and adding.

about 0.1-0.6 parts of wax (camauba wax, parafiin wax. or a mixture thereof) per part of the polyfunctional component (polyene) thereto while vigorously agitating the resulting third mixture and maintaining it at ca. 8090C. I prefer to add the wax in the molten state or as small (ca. minus about 4 mesh) chips or as powder (ca. minus about mesh) but larger particles of wax can be added.

a. Where including beeswax in the composition I prefer to admix it (the beeswax) with the other wax (carnauba wax, paraffin wax, or a mixture thereof) and add the resulting mixed wax to the second mixture prepared in step 2. supra.

b. Where including paraffin oil and/or silicone oil (silicone fluid) in the polishing wax of this invention I can admix the paraffin oil and/or silicone oil with the wax and add the resulting mixture of oil and wax to the second mixture prepared in step 2. supra. However. the oil per se can be admixed the third mixture before adding the polythiol thereto. or to the fourth mixture, infra. or to the fifth mixture, infra.

. Where including glycerol (ora glycol) in the polishing wax of this invention the glycerol can be added to the third mixture. Alternatively, the glycerol can be admixed with the water before adding the water to tlie first mixture.

4. Maintaining the third mixture at about 80-90C.

and agitating it vigorously while adding the aforesaid polythiol tliereto in an amount to provide. in the resulting fourth mixture about 0.6-1.1 equivalents of thiol' per equivalent of polyfunctional compound, and continuing to agitate the resulting fourth mixture vigorously while maintaining said fourth mixture at about 80-90C.

5. Maintaining the fourth mixture at about 80-90C. and agitating it vigorously while adding thereto about 0.05-0.25 part of the photocuring rate accelerator (said rate accelerator being added in the liquid or molten state) per part of the polyfunctional component while vigorously agitating the resulting fifth mixture and maintaining it at about 8090C.

6. Cooling the fifth mixture (the photocurable polishing wax of my invention) to about 20-30C. (preferably over a period of about 0.5-2 hours) while continuing to agitate it.

While the above procedure is the preferred method for preparing my photocurable polishing wax composition it is not the only procedure by which said composition can be prepared. For exampie; (a) the photocuring rate accelerator can be added as a fine powder (e.g., minus ca. 200 mesh or finer) or it can be dispersed in the water and added with the water; (b) the polythiol can be admixed with the system before or after adding the water; (c) if the polyfunctional compound and the polythiol are admixed before the water is added the polythiol can be admixed into the system before or after the emulsifier is admixed into the system; (d) the emulsifier must be present in the system when the water is added thereto; and (e) the wax can be added before or after adding the polythiol.

Various other modifications W31. because of my disclosure, be readily apparent to those skilled in the art. l have found that it is important that the water be added 'to a mixture comprising at least the polyfunctional compound and the emulsifier rather than; (a) adding the polyfunctional compound and the emulsifier to the water, or (b) adding the polyfunctional compound to a mixture comprising the water and the emulsifier. l have also found that it is important that the mixture to which the water is added should contain the emulsifier and agitated vigorously whfie adding the water thereto.

One skilled in the art can readfiy determine the degree of agitation which is sufficiently vigorous for this purpose because the desired emuision will not form if agitation is not sufficiently vigorous. it is also important that the water be added in relatively small increments (ca. 0.1-0.3 or 04 part per part of the polyfunctional component) because if too much water is added at one time (or; if the increments are added too close together) the desired emulsion will not fortn. Because of my disclosure one skilled in the art can readily determine the proper increment size and the prop-er period of time between increments. Alternatively, the second mixture can be formed by slowly adding the water as a small continuously flowing stream.

If desired. about 5-25 percent of a water insoluble. abrasive. particulate filler (based on the weight of photocurable polishing wax plus said filler) can be incorporated into the photocurable polishing wax at any step during the preparation of said wax.

tion, the composition will cure (polymerize) on exposure to actinic radiation.

Among the polyenes which have been used to prepare the photocurable polishing wax of this invention are:

l. A triene (designated "T-l which has the formula was prepared by admixing and reacting equal molar mole basis) with a polyethylene glycol having the forquantities (e.g l mole of each) of toluene diisocyamula nate. trimethylol propane diailyl ether, and ally! alcoz r' fi i hol. About 0.! g of dibutyl tin dilaurate was present to in which m is average numb R were m d catalyze the reaction. Said tricne (T-l) produced pho- 5 using polyethytene g t i hi h m was 2, 1t 19 wguwblc Polishing of excellent q y and 37. Each diene (each diene designated T-S) made 4. o-, m. and p-diallyl phthalate (all designated f a polyethylene glymt h -g one Qfgaid values for "T-2 and mixtures of any two (and all three) of m was d to p palrg a hotocurable polishing wax of isomeric phlhalales were used to Prepare the this invention and each such wax was an excellent polpolishmg wax of my invention. in each instance the m ishing wax f poqgshing t urfages including autophotocurable polishing wax was a polishing wax of mobfle bodies excellent qualilyj 6. A tetraene (designated T-6") was prepared by; 3. A tetraene (designated T-3") which has the for- (a) admixing and reaming 2 moles of mula isocyanatomethyl-3.5,S-trimethylcyclohexylisocyanate (lPDl) and one mole of a polyethylene glycol having an average molecular weight of about 400 to form one mole of intermediate compound CH: 0 i it having two. isocyanate grocps per molecule; and f i if i (b) admixing and reacting 5 mole of said intermeiO'F diate and two moles of trirnethylol propane diallyl ether to form the tetraene desigzated T-6. if de- COC1l' (.'-H=Cl[= sired about 0.4 g of dibutyl tin dilaurate can be H 2 added to catalyze the reaction between the isocyanate radicals and the hydroxyl groups of; (a) the polyethylene glycol; and'fla) the trimethylal pror pane diallyl ether. This tetraene was used to prewas prepared by: i 'ying malic acid will! all?! pare the photocurable polishing wax of the instant alcohol to form diallyl malate; and (b) reacting 2 moles invention, The resulting wax was a polishing wax of of the diallyl malate with one moie of toluene diisocyax llent quality well adapted for polishing autonate. About 0.2 g of dibutyl tin dilaurate can be used mobile bodies. i as catalyst where using 1 mole of toluene diisocyanate. 7. A tetraene (designated T-T') was prepared by; Said letracne as used to prepare the photocur- (a) admixing and reacting 2 moles of toluene diisoaole polishing wax of this invention. The resulting wax cyanate and one mole of diel-hydroxyethyhdimewas a polishing wax of excellent quality. thylhydantoin (DHM) to fem 1 mole of an inter- 4. A diene (designated "T4"; which has the formula mediate compound having two isocyanate groups ctr, Cm

I n 0 v ll 1! o=c-N t tt-o-cnsctnocttscm-o-c-t z N-( 3=0 o r (in: on: en ti EH: i l"! was prepared by admixing and reacting 2 moles of tolu- (radicals) per molecule; and (b) admixing and reene diisocyanate, l mole of diethylene glycol and 2 acting l mole of said intermediate and two moles moles of allyl alcohol. About 0.4 g of dibutyl tin dilauof trimethylol propane dialyl ether to form the rate can be added as catalyst. Said diene (T4) was tetraene designate T-7. if desi 13-0- 3 used to prepare the photocutable polishing wax of my of dibutyl tin dilaurate can be used to catalyze reinvention. The thus prepared wax was an excellent polaction of lhe isocyanate E P m6 ydr xyl i hi w groups of the DHM and the trimethylol propane 5. Other dienes (designated T-S") and having the diaiiyi This P y (T3) was found 10 b6 formula excellently adapted for preparing the phoiocurable CH1 (3H1 ill I 3 t f 1! i l =c-x 3- 412m -ocu,ct|-o-c t'-z N-(-=0 1 i 0 V. I, o I ll CH] tilt itl (iii; *M C":

were prepared according to the general procedure used i hi wax f hi i mg d h wax 10 P p {he dime dfilgnaled T4; however. Where pared with T-7 was a wax of excellent quality well preparing a diene to be designated T-S. the diethylene d md f li hi mobile b di s, d 1h glycol used to prepare T4 was replaced (On a mOl fo metal surfacesl 8. A tetrane (designated T-t) was prepared according to the general procedure used to prepare the tetraene which was designated T-7. However. in this instance, the procedure was modifying by replacing the 2 moles of toluene diisocyanate which was used to prepare polyene T-I with 2 moles of the above described lPDl (which was used to prepare the tetraene designated T-6). The resuiting tetraene (T8) was excellently adapted for use in preparing the photocurable polishing wax of my invention. and wax prepared with tetraene T-8 was of excellent quality, being well adapted for polishing automobile bodies and other metal surfaces. 9. A triene (designated "T-9") was prepared by ad- 12 l l. A polythiol (designated "P-l l") was prepared by the process used to prepare P-7 but modified u replacing the 3-mercaptopropionic acidwith 2-mercaptoacetic acid. l2-l4. Polythiols (designated P-l 2", and P-l3 P-l4") were prepared by the general method used to prepare P-ll except that to prepare; (a) p-l2. 2 moles of stearic acid (or its acid chloride) were use; (b) P-l3. 3 moles of stearic acid (or its acid chloride) were used; and (c) P44, 4 moles of stearic acid (or its acid chloride) were used.

l5. A polythiol (designated P4 5) was prepared by reacting (esterifying) all 6 OH groups of DPE with 3-mercaptopropionic acid.

mixing 272 g of pentaerythritol and [300 g of a i5 16. Apolythioi (designated P-l6)was prepared by 50% sodium hydroxide solution and adding thereto reacting (esterifying) all 6 OH groups Z-mercap- 1936 g of allyl bromide while maintaining the retoacetic acid. suiting mixture at 70-80C for about 12 hours. J17. Apolythiol (designated P-l7") was prepared by The product ("f-9) was identified as the triallyl reacting bisphenol A with propylene oxide (2 ester of pentaerythritol. it was used to prepare the moles of said oxide per mole of bisphenol A) and photocuring polishing wax of my'invention and said esterifying the resulting glycol with 3-mercaptoprowax was found to be excellently adapted for polishpionic acid. ing automobile bodies. 18. A polythiol (designated "P-l 8") was prepared by Among the polythiols which have been used to prethe procedure used to prepare P-l7 except that the pare the photocurable polishing wax of this invention B-mercaptopropionic acid was replaced with are: Z-mercaptoacetic acid. l. Trimethylol propane tris (3-mercaptopropionate) 19. A polythiol (designated P-l9") was prepared by which is designated P-l". reacting the above-described T-Q with a stoichio- 2. Trimethylol propane tris (2-mercaptoacetate) metric amount of thiolacetic acid (3 moles of said which is designated P-2". acid per mole of T-9) in the presence of a catalytic 3. Pentaerythritol tetrakis (B-mercaptopro pionate) amount of t-butyl hydroperoxide. Reaction temwhich is designated P-3". perature was about 8090C. The reaction prod- 4. Pentaerythritol tetrakis (wmercaptoa'cetate) was uct was admixed with aqueous sodium hydroxide designated P-4". (using 2.5 equivalents of said hydroxide for each 5. Tris( Z-hydroxyethyl)isocyanurate tris( 3-mercapequivalent of T-9 feed refluxed for about 3 hours, topropionate) was designated "P-S"; it was -made by cooled and extracted with ether. The product the procedure taught by U.S. Pat. No. 3.676.440 (Los. which was recovered from the ether was identified 260/248). as

6. Tris( 241 yd roxyethyl )isocyanu rate tris( 2- mercaptoacetate) which was designated P-6 was 40 CHaO cincmcmsu prepared by the general procedure used to prepare n cmc-cr ocmemcmsu' PS. but said procedure was modified by replacing c ,OCHCHICHS the 3-mcrcaptopropionic acid with Z-mercaptoafl acid- The instant invention will be better understood by re- 7- A polyth l ("P- was p p r y; i yferring to the following specific but nonlimiting examing one I of the OH groups of dipentaerythritol pies. it is understood that said invention is not limited With Static acid with the ac Ch oride by these examples which are offered merely as illustraf made ci to form n intermediate; n tions; it is also understood that modifications can be m sterifying the c a fl g 5 OH gr p of {ht made without departing from the spirit and scope of the intermediate with 3-mercaptopropionic to form so invention, polythiol P7. 8. A polythiol ("P-8) was prepared by; (a) esterify- EXAMPLE I ing two of the OH groups of DPE with stearic acid A diene having the formula (or the acid chloride thereof l according to the general procedure used to prepare T-7 but moodifying said procedure by using with two moles of stearic it acid (or its acid chloride) per mole of DPE; and (b) C r= IlC h0- lN- then esterifying the remaining 4 OH groups with 3-mercaptopropionic acid to form polythiol P-8. 0 9. A polythiol P-9") was prepared by the method li used to prepare P-8 except that 3 moles of stearic acid (or its acid chloride) and 3 moles of 3mercaptopropionic acid were used per mole of DPE. 10. A polythiol (designated "P-lO) was prepared by was prepared by reacting allyl alcohol with a stoichiometric quantity of 4.4'-dicyclohexylmethane diisocyanate (2 moles of the alcohol per mole of the diisocyahate) in the presence of 0.2 g of dibutyl tin dilaurate catalyst in a resin kettle while maintaining the reacting the method used to prepare P-S except that 4 moles of stearic acid (or its acid chloride) and 2 moles of B-mercaptopropionic acid were used per mole of DPE.

EXAMPLE 2 A tetraene designated Product 2" was prepared by the following method:

Five moles of Epon 828 (a epoxy compound (obtained from Shell Chemical Co.) having the formula I c OCll CH-Cll: C) CH:

in whichAis CH5 on I .9?

.- and n is a number greater than and less than I and having an average value such that the average molecular weight of the epoxy compound is about 390) and twelve moles of diallylamine were admixed under an atmosphere of nitrogen and maintained at about 80-90C- (under said atmosphere oinitrogen) for about 2-3 hours. Then unreacted diallyl amine was distilled off under reduced pressure (ca. l-lO mm of mercury absolute) and the residue (substantially-pure Product 2) was recovered. *2-

EXAMPLE 3 A l00 g portion of Product l (the diene prepared in Example 1 was heated to about 90C. and 50 g of Pluronic F88 (a nonionlc emulsifier resulting from the action of ethylene oxide and polypropylene glycol) was added thereto to form a first mixture. The first mixture was stirred vigorously and 500 g of water having a temperature of about 90C was added thereto in about 20 ml increments over a period of about an hour while vigorously stirring the first mixture and the resulting second mixture and while maintaining the temperature thereof about 90C. A 50 g portion ofa mixture of carnauba wax and paraffin wax (melting at about S5-60C.) was added to the second mixture while tigorously stirring the second mixture and the resulting third mixture and while maintaining the temperature thereof at about 90C. The wax mixture (eaual parts by weight of earn-.uba wax and paraffin wax) was added as a powder passing an eight mesh screen. A 64 q portion of pentaerythritol tetrakis (B-mercaptoprm pionate) was added to the third mixture while vigorously stirring the third mixture and the resulting fourth 90C. to about 25"C. over a period of about 2 hours. The thus formed was: (which was degnated Product 3") was packaged in a light proof container and the container was closed with a ligzlt proof closure.

A thin coating of the above describedphotocurable polishing wax (Product 3) was applied to the surface of an aizwmobile bod using a corrrentioral waxing technique except that the war was zpphed and rubbed into a smooth coating while the automobile was in a garage where it was protected from stmlight and other actinic radiation.

After applying the wax and rubbing it smooth the automobile was placed in direct sunlight. in about l0 minutes bc wax coating hardened into hard. scratch resistant. transparent finish which om bul'tfng became very srnoo th and glossy. when driveng in bad weather (ineluding snow and rain) this was coatletg held up better and retained its @pearance better than a coating of conventional automobile wax.

EXAMPLE 4 Tim general procedure used to prepare product 3 was repeated. However. in this insmce tie procedure was modified by heat'mg the diene (Product X) to 80C.

EXAMPLE 5 In another run the general procedure used to prepare Product 3 was repeated. However. in this instance the procedure was modified by adding 183 g of particulate calcium carbonate .1 which passed a 200 mesh screen) to the vigorously stirred third mixture before adding the polythiol therew (the temperature of the third mixture being maintained at about QOC- while adding the mixture and while maintaining the temperature thereof at about C. An 8 g portion of molten benzophenone (a photocuring rate accelerator) was added to the fourth mixture while vigorously stirring the fourth mixture and the resulting fifth mixture (the photocurable wax of my invention) and while maintaining the temperature thereof at about 90C. While stirring the Fifth mixture it (the fifth mixture) was cooled from about particulate calcium carbonate thereto}. The resulting product (Product 5) was found 10 be a superior photocuring polishing wax when applied to an automobile bod cured in sunlight. and buffed after curing.

Excellent photocurable polishes, cash of which gave cxceilent results where applied to an automobile body. cured. and buffed after curing. were also obtained in other runs in whfich the calcium tzrbonate was replaced with -480 g portions of various other partic' ulate fillers (including those Lsted in the above Description of Preferred Embodiments} passing a 325 mesh screen.

EXAMPLE 6 The general procedure used to prepare Product 3 was repeated. However, in this instance the procedure was modified by replacing the (lien: (Product I used in Example 3 with the tetraene (Product 2) prepared in Example 2. lr. rlnis instance 55 g ct pentaerythritol tetraiais (B-mercapeopropionatei was used.

The resulting product (Product 6f: was a photocurable polishing wax. of high quality excellently adapted.

for use as a polishing wax for automobiles. metal surfaces and wooden surfaces.

EXAMPLE 7 The general procedure of Example 6 was repeated. However, in this instance the pentaerythritol tetra zis B-mercaptopropionate) was replaced with 90 g of eth ylene glycol (fi-mercaptopropionate).

The resulting product (Product 7) was a photocurable po ishing wax of high quality excellently adapted for use as a polishing t -ax for automobiles.

EXAMPLE 8 A tetraene having the formula C1110 CILCH=CH1 was prepared by admixing 2 moles of trimethylol propane diallyl ether and 0.2 g of dibutyl tin dilaurate as a catalyst in a resin kettle. The mixture was kept EXAMPLE 9 A 100 g portion of Product 8 (the tetraene prepai ed in Example 8) was heated to about 90C. and 100 g of Pluronic F88 (a nonionic emulsifier resulting from the action of ethylene oxide and polypropylene glycol) was added thereto to form a first mixture. The first mixture was stirred vigorously and 380 g of water having a temperature of about 90C was added thereto in about m! increments over a period of about an hour while vigorously stirring the first mixture and the resulting sec ond mir'ture and while maintaining the temperature thereof about 90C. A 50 g portion ofa mixture of carnauba wax admixed with a g portion of beeswax was added to the second mixture while vigorously stirring the second mixture and the resulting third mixture and while maintaining the temperature thereof at about 90C. The wax mixture was added as a powder passing an eight mesh screen. A 60 g portion of pentaerythritol tetrakis (B-mercaptopropionate) was added to the third mixture while vigorously stirring the third mixture and the resulting fourth mixture and while maintaining the temperature thereof at about 90C. An I l g portion of molten benzcphenone (a photocuring rate accelerator) was added to the fourth mixture while vigorously stirring the fourth mixture and the resulting fifth mixture and. while maintaining the temperature thereof at about 90C. a g portion ofsilicone oil (Dow Corning Silicone Fluid No. 550) was added to the fifth mixture while vigorously stirring the fith mixture and the resulting sixth mixture and while maintaining the temperature thereof at about 90C. While stirring the sixth mixture it (the sixth mixture) was cooled from about 90C to about 25C over a period of about 2 hours. The sixth mixture. 21 photocurable waxy of my invention, was designated Product 9". Said Product 9 packaged in a light proof container was closed with a light proof closure.

A thin coating of the above described photocurable polishing wax (Product 9) was applied to the surface of an automobile body using a conventional waxing tech nique except the the wax was applied and rubbed into a smooth coating while the automobile was in a garage where it was protected from sunlight and other actinic radiation.

After applying the wax and rubbing it smooth the autorhobile was placed in direct sunlight. in about 10 minutes the wax coating hardened into hard. scratch resistant. transparent finish which on buffing became very smooth and glossy. When driving in bad weather (including snow and rain) this wax coating held-up better and retained its appearance better than a coating of conventional automobile wax.

EXAMPLE 10 The general procedure of Example 3 was repeated. However. in this instance the procedure was modified by replacing the diene (Product l) used in Example 3 with the tetraene (Product 8) prepared in Example 8. ln this instance 8l g of pentacrythritol tetrakis (B-mercaptopropionate) was used.

The resulting product (Product 10) was a photocur able polishing wax of high quality excellently adapted for use as a polishing wax for automobiles. metal surfaces and wooden surfaces.

in other runs (Runs l-7 reported below) using the a. U.S. Pat. No. 3.615.450. Werber et al, 96/35.l.

b. U.S. Pat. No. 3.645.730. Frank ct al. 96/28.

c. U.S. Pat. No. 3.537.853. Wessells et al. 96l35.l.

d. U.S. Pat. No. 3.535,l93. Prince. 161/88.

e. U.S. Pat. No. 3.66l .744. Kehr et al, 204/159. 14.

f. U.S. Pat. No- 5.578.6l4. Wazolek. 260/13.

g. U.S. Pat. No. 3.660.088. Lundsager. 961/36.

h. U.S. Pat. No- 3.662.022. Lard. 260/837 R.

i. U.S. Pat. No. 3.662.023, Kehr et al. 260/850.

j. U.S. Pat. No. 3.700.574, Kehr et al, 204/l59.l4. 0

in each instance care was used to match the polyfunctional component with a polythiol that would assure a total functionality (the functionality of the polyene and the polythiol) greater than 4.

2. The polythicl (pentaerythritol tetrakis (B-mercaptopropionate)) which was used in Example 3 was replaced with each of the polythiol components having molecules containing at least two thiol groups per molecule which are taught in said above-mentioned patents and by [.35. Pat. No.

3.676.440 (Los, 260/248NS). using care to match the polythiol with a polyfunctional compound (polyene) so that the total functionality of the resulting mixture was greater than 4.

. The benzcphenone (photocuring rate accelerator) used in Example 3 was replaced with the photocuring rate accelerators taught in said abovementioned U.S. Patents using amounts of photocuring rate accelerator varying from about 0.05 to about 0.25 part or more (preferably 0.05-0.15 part) of photocuring rate accelerator per part of polyene.

4. The emulsifier used in Example 3 was replaced with the nonionic emulsifiers listed on pages 128-l 30'of volume 8 of the Second Edition i965) of Othmer. Encyclopedia of Chemical Technology." These runs were made using 0.2. 0.3, 0.6, l and L5 part of emulsifier per part of polyene.

5. The carnauba waxparaffin wax mixture used in Example 3 was replaced with; (a) caranauba wax; (b) paraffin wax. and (c) mixtures of 0.1, 0.2, 0.5, l. 5. l0. and 20 parts of paraffin wax per part of camauba wax. These runs were made using 0.1. 0.3. 0.6. and 0.9 part of the wax. per part ofthe polyene.

6. The "quantity of water was varied using -l. 2. 3. 4, 5. l0. oxide. magnesium oxide. calcined dolomite. calcium hydroxide. hydrated 40. and 50 parts of water per part of the polyfunctional compound containing at least two ethylenically unsaturated bonds per molecule.

7. A large number of particulate water insoluble abrasive fillers including particulate dolomitexalcium phosphate, calcium hydroxide. hydrated magnesium oxide. hydrated calcined dolomite, clay,

talc, mica. silica. alumina. titania. gypsum. glass. and the like. the particles being of such size that they passed about a l mesh screen (or a 200 mesh screen or a 325 mesh screen) were used in place of the calcium carbonate of Example 5. The quantity of filler used included 5. i0. 20. and 25 percent based on the weight of the photocuring polishing wax plus filler. Mixtures of these fillers were also used keeping the total amount of filler within the above-mentioned range (-25 percent calculated on the above-named basis).

Each composition prepared in the above-mentioned runs (Runs 1-7) was a high quality photocurable polishing wax which was excellently adapted for polishing automobile bodies and other metal or wooden surfaces.

When preparing each composition (photocurable polishing wax) reported in said Runs l-7; (a) the polyene and polythiol used were always selected so that the total functionality (that of the polyene plus that of the polythiol) was greater than 4; and (b) the equivalent ratio of polyene to polythiol was maintained within the range of l:0.6l.l.

EXAMPLE ll Run No. l: A photocurable wax was prepared according to the general procedure of Example 9. However. in this run the procedure wa modified by using the following materials in the quantities set forth below:

100 g of the tetraene prepared in Example 8 100 g of Pluronic F88 (a nonionic emulsifier) 380 g of water 50 g of camauba wax admixed with 4l g of bees wax and 82 g of silicone oil having a viscosity of 125 centistokes (specific gravity 1.07) at 25C 60 g of pentaerythritol tctrakis (fi-mercaptoproabout l0 minutes. The thus polished and cured surface of the test strip had a bright glossy appearance. Water applied to the waxed surface as a spray formed beads which ran off (i.e., the water did not form an aqueous film on the waxed surface)- The polished and cured test strip was subjected to a weather sensitivity test using a commercially available Xenotest appliance (obtainable from Carl Zeiss, Inc., 444 Fifth Avenue. New York. N. Y. l00l8). in this test the waxed surface was continuously exposed to actinic light having wave lengths corresponding to those of actinic sun light while being inten'nittently subjected to a water spray. The spray cycle was one-half hour on and one'half hour off.

After 170.3 hours testing the waxed surface still had a glossy appearance. and water applied to the Waxed surface as a spray formed beads which ran off.

Run No. 3: A second test strip from the same lot as that used in Run No. 2. supra, was coated with a film of a first commercially available automobile polishing wax (J Wax) which was polished by rubbing with a clean soft cloth. The polished waxed surface had a bright glossy appearance. and water applied thereto as a spray formed beads which ran 05.

The polished waxed surface was subjected to the above-described weather sensitivity test. After "59.5 hours testing the surface no longer appeared glossy. Water applied to the tested surface as a spray did not form beads; it coated the tested surface with a film of water.

Run No. 4: The general procedure of Run No. 3, supra. was repeated. However. in this instance the procedure was modified by replacing the first commercially available automobile polishing wax with a second commercially available automobile polishing wax (Simonize). The polished waxed surface had a bright glossyappearance, and water applied thereto as a spray formed beads which ran off.

The polished surface was subjected to the above described weather sensitivity test After 169.5 hours testing the surface had only a slight gloss. and water applied thereto as a spray did not form beads. On the contrary, the water spray coated the tested surface with a film of water.

EXAMPLE 12 A series of photocurable polishing waxes of my in vention were made in a series of runs (reported in the following table) using the general procedure of Example 3. However. in the runs of this example said procedure was modified by using. in the respective run. the polyene listed t it! said table) for such run and the polythiol listed (in said table) for such run. In each run the total functionality (that of the polyene plus that of the polythiol) was always greater than 4.

in each run a 100 g portion of polyene was used and the quantity of polythiol was so selected that the equivalent ratio of polyene to polythiol was l:O.6-l.l.

The photocurable polishing wax made in each of said runs was used to polish a painted outside surface of an automobile body. The wait gave an excellent polish which remained in good condition during a 9 month test period each of said automobiles being driven regularly (at least 200 miles per week in the Washington Baltimore area.

PREPARATION OF PHOTOCURABLE POLISHING \VAX Run No. Polyene Polythiol Equivalent Ratio of Po yenezPolythiol 2 T-l P-Z 1:0.8 3 T-l P-3 l:0.7 4 (a) T-2 (a) P-4 l:0.6 5 (b) T-Z (b) P-S l:l.l 6 (c) T-2 (c) P-5 1:0.95 7 T-3 P 6 120.65 8 -T-3 P-lO 110.85 9 T-4 P-6 l:l l (d.cl T-S (d.e) P-7 l:l

ll T-6 P-7 1:! l2 T-7 P-B l:0.7 l3 T-8 E8 lzOJ 1 l4 T-9 P-B 1:0.75 l5 (fl T-2 (f) P-ll 1:0.6 l6 T4 P-9 l:0.65 l'l T-l P-lO l:0.6 l8 T-7 9-12 l.'l.l l9 T-J F-l3 l:l.05 20, T-6 P-H l:0.8 2| (f) T-2 (fl P-lS l:0.7 22 Ml 9-16 L019 23 T4 P-l7 It! 24 T-l P- l 8 l:0.9$ 25 T4 P-l9 l:0.85 26 T-l 9-9 l:0.7$ 27 T-! P-lO l 0.65 28 (f) T-2 (f) P42 l:0.6 29 T4! P-l9 Hi] 30 T-9 P-l9 l:0.8 3! (g) T-2 (g) P-3 1:! 32 (h) T-2 (h) P-lS III 33 (i) T-2 (i) P-l6 lzl la) The polyene as u-diallyl phthahtc.

(M The polycrw as p-diallyl phthahlc.

(cl The pulycne has m-diallti phthalatc.

rdl In thirrun Run Nu. mi m \as 2. (Sec the description: of polycne (-5. ml tel Hun it! was made using punts: "(-5 in which "at" a 2. then replication: of this run were nude in uhich the pmccdurc was modified by using T-S poho'cl in which n-i" a! 2. H. l9. and 37. In each instance the resulting photuc -rng polishing wait s n was of excellent quality ncclkndy adapted for polishaq. automobiles and other metal surfaces.

(0 The polgenc a a mixture of 0-, nt-. and p-dialtyl pbthalate.

(I The polgene a: a mixture of tinnd m-diallyl phthabtc.

(hi Tm: poly-en: as a mixture of 0- and p-diallyl phtlubtc.

(it The pulyenc on a mixture of mand p'diallyl phthalak.

Further runs (each preparing the photocurable polishing wax of my invention) were made using the general procedure of Example 3. However. in these runs said procedure was modified by replacing the polyene and polythiol of Example 3 with a polyene and a polythiol selected from the above table. At least one run was made wherein each polyene in said table was matched with each polythiol in said table-except that no run was made wherein a dicne was matched with a dithiol. In each run the product was a photocurable polishing wax excellently adapted for polishing auromobile bodies and other painted metal and wooden surfaces.

As used herein the term polyene refers to single or complex species of alkenes, solid or liquid at or below C. having a multiplicity of terminal reactive carbonto-carbon unsaturated functional groups per average molecule. For example, a diene is a polyene that has two reactive carbon-to-carbon double bonds per averge molecule.

The term functionality as used herein refers to the average number of ene or thiol groups r molecule in the polyene or polythiol. respectively. For example. a triene is a polyene with of three "reacti e" carbon-tocarbon unsaturated groups per molecule and thus has a funct onality of three. A dithiol is a polythiol with two thiol groups per molecule and thus has a functionality of two. A trithiol has a functionality ofthree. and a tetrathiol has A functionality of four. A diene has a functionality of two, and a tetraene a functionality of four.

' As used herein the term react-Eve" :5 applied to the polyftmctional compound or component (the polyene) containing at least two ethylenically unsaturated carbon-to-carbon bonds per molecule means that the unsaturated carbon-to-carbon boni will react under the conditions as set forth with thiol groups to yield the thioether linkage v as contrasted to the term unreactive carbon-to-carbon unsaturation which means groups found in aromatic nuclei (cyclic structures exemplifred by benzene. pyridine. anthracene, andthe like) which do not under the same conditions react with thiol groups to yield the thioether linkage.

The term equivalent as applied to a polythiol means that quantity of the polythiol which contains 33.07 grams of -SH group. Thus. an equivalent of pentaerythritol tetra-beta-mercaptephopionate is onequarter mole of said mercaptopropionate because each molecule of said mercaptopropio-nate contains 4 SH groups (i.e., a mole of this compound contains 132.28 grams of -SH In a polythiol compound having the formula RrOiL-Re- H) in which R and R, are hydrocarbyl moieties (or radicals) an equivalent is one-half mole where n is 2; onethird mole where n is 3, one-quarter mole where n is 4 and one-fifth mole where n is 5- As noted supra, the term reactive ethylenically un saturated group" means a group (hating olefinic car bon-to-carbon unszruration) which will react under proper conditions as set forth herein with thiol groups to yield a thioether linkage as contrasted to the term unreacti e carbon-to-carbon unsaturation" which means groups found in aromatic nucleii (cyclic structures ex emplified by benzene. pyridine. anthracenc. and the like) which do not under the same conditions react with thiols to give thioether linkages.

The term "equivalent" as applied to a compound having reactive olefinic unsaturation means that quantity of the compound which contains one reactive olefinic double bond. Thus, if a compound contains two such bonds an equivalent of said compound is one-half mole of said compound, while an equivalent of a compound containing 3 such bonds is one-third mole, and an equivalent of a compound containing 4 such bonds is one-quarter mole.

As used herein, the term percent" means parts per hundred and the term parts" means parts by weight unless otherwise defined where used.

As used herein, the termfmolel has its generally accepted meaning. that is. a mole of a substance is that quantity of the substance which contains the same number of molecules of the substance as there are atoms of carbon in 12 grams of pure C.

As used herein, the term g means gram or grams.

As used herein. the term A means Angstrom units.

As used herein, the term mesh." as applied to screen size, means U.S. standard.

As used herein. the term ml means milliliter or milliliters.

As used herein. the term fmil" means 0.001 inch; thus, 10 mils is 0.01 inch and 100 mils is 0.1 inch.

whc rein js and n has an average value such that the average molecular weight of the polyene is about 584; i

b. about 0.2-1 part of a nqnionic emulsifier;

c. about 0.1-2 parts of a wax selected from the group consisting of camauba wax, a paraflin'wax melting at about 43-68C. or a mixture thereof;

d. about 1-50 parts of water;

I claim: e. a quantity of a polythiol having molecules contain- 1. A photocurable polishing wax consisting essening at least two thiol groups per molecule to protially of a mixture of: vide about 0.6-1.1 equivalent of polythiol per a. 1 part of a polyene having the formula; equivalent of the polyene, the total functionality of ([311; m it o o I l r t o=r -2 :-b-o-cu:cinocn,cm-o-e-N N(|3=0 o 0 (En 4:11: 1 CH H: i lthe polyene and the polythiol being greater than 4; u ir-o-cm clt=cn, 45 and 1O L J f. 0.05-0.25 part of a photocuring rate accelerator.

2. The composition of claim I in which said composition contains about 5-25 percent by weight of a water insoluble, abrasive. particulate filler based on the weight of the photocurable polishing wax plus filler, the

particulate filler being of such size that it will pass about a I00 mesh screen.

3. The composition of claim 1 in which the photocuring rate accelerator is selected from the group consisting of an aryl aldehyde, a diaryl ketone. at dialkyl ketone. an alkyl aryl ketone. 21 triaryl phosphine, and a blend of a carbon tetrahalide with a polynuclear aromatic hydrocarbon.

4. The composition of claim 1 in which the wax is carnauba wax.

5. The composition of claim I in which the wax is paraffin wax.

6. The composition of claim 1 in which the wax is a mixture of carnauba wax and paraffin wax.

7. The composition of claim 1 in which photocuring rate accelerator is benzophenone.

8. The composition of claim 1 in which the polyene 1S 9. The composition of claim 1 in which polythiol is 5 pentaerythritol tetrakis (fi-mercaptopropionate).

10. The composition of claim 1 in which nonionic emulsifier is a polyoxypropylene-polyoxyethylene.

ll. The composition of claim 1 in which the polyene m CHzO ClhCH=Clh ,QLHLW L on, cmocmcu=cm 12. The composition of claim 1 in which there is about ODS-0.1 part of photocuring rate accelerator per part of the polyene.

13. The composition of claim 1 in which water content of the photocurable polishing wax is about 2-10 parts per part of the polyene.

14. A photocurable polishing was; consisting essentially:

a. 1 part of a polyene having the formula C l'h QhOCECH=CH= may UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 853,728 Dated December 10 1974 Inventor(s) Josenh Francis Wrzesinski It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Change the formula in line 55 of column 21 from Nd- 0-CH CH=CH Change the formula in line 65 of column 21 from oce m cn, G

OCH -i mg?" UNITED STATES PATENT OFFICE Page CERTIFICATE OF CORRECTION 25 Patent No. 3,853,728 Dated December 10', 1974 Inventofls) Jose'oh Francis Wrzesinski It is certified that error appears in the above-identified patent: and that saidi Letters Patent are hereby corrected as shown below:

r Change the formula in line 6 6f column 22 frem n nt 0 cH cE=cI 5 Delete the formula. in line 11 of column "22 Change the formala in line 16 of column 22 from @wcu ilcu j i oo-ca lz-cn Signed and sealed 'this 6th day of May 1975.

(SEAL) Attest:

C.- MARSHALL DANN RUTH C. MASON Commissioner of Patents Arresting Officer and Trademarks 

1. A PHOTOCURABLE POLISHING WAX CONSISTING ESSENTIALLY OF A MIXTURE OF: A. 1 PART OF A POLYENE HAVING THE FORMULA;
 2. The composition of claim 1 in which said composition contains about 5-25 percent by weight of a water insoluble, abrasive, particulate filler based on the weight of the photocurable polishing wax plus filler, the particulate filler being of such size that it will pass about a 100 mesh screen.
 3. The composition of claim 1 in which the photocuring rate accelerator is selected from the group consisting of an aryl aldehyde, a diaryl ketone, a dialkyl ketone, an alkyl aryl ketone, a triaryl phosphine, and a blend of a carbon tetrahalide with a polynuclear aromatic hydrocarbon.
 4. The composition of claim 1 in which the wax is carnauba wax.
 5. The composition of claim 1 in which the wax is paraffin wax.
 6. The composition of claim 1 in which the wax is a mixture of carnauba wax and paraffin wax.
 7. The composition of claim 1 in which photocuring rate accelerator is benzophenone.
 8. The composition of claim 1 in which the polyene is
 9. The composition of claim 1 in which polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).
 10. The composition of claim 1 in which nonionic emulsifier is a polyoxypropylene-polyoxyethylene.
 11. The composition of claim 1 in which the polyene is
 12. The composition of claim 1 in which there is about 0.05-0.1 part of photocuring rate accelerator per part of the polyene.
 13. The composition of claim 1 in which water content of the photocurable polishing wax is about 2-10 parts per part of the polyene.
 14. A photocurable polishing wax consisting essentially: a. 1 part of a polyene having the formula 